Enclosure 1

Instructions for Sample Collection, Packaging, and Shipment

EPA Sampling Program

The samples you will be collecting are very important. The samples will be used by the U.S. Environmental Protection Agency (EPA) for revising th e effluent limitations guidelines and standards for the Steam Electric Power Gen erating Industry.

These instructions are being provided to Duke Energy Carolinas’ Belews Creek Steam Station to aid in collecting, packaging, and shipping sample s for this sampling program.

The plant must collect grab samples for all analytes a t the influent to the FGD wastewater treatment sampling point and 24-hour composite samples for all analytes except mercury and cyanide at the bioreactor influent and bioreactor efflue nt sampling points. At the bioreactor influent and bioreactor effluent, the plant must collect cyanide as a single grab sample and mercury must be collected as four individual grab samples over the 24-hour period (i.e., a grab sample collected every six hours).

Samples will be collected once a month for four month s. The samples should be collected and shipped to the laboratories according to the schedule provided in the cover letter of this request. If the plant has any questions re garding the timeline or the steps provided, please contact Mr. Ronald Jordan at (202) 566-1003 or j ordan.ronald@epa.gov.

Equipment Needed

The plant will need to obtain the following equipment to collect, pack, and ship the samples to the laboratories:

• Sample bottles, composite containers, and tubing sets (spe cially-cleaned according to EPA Method 1669);

• Automatic compositor;

• Powder-free gloves;

• Tyvek® coveralls or suitable alternative;

• Dust masks (for use while collecting mercury samples)

• Labels (for sample bottles and shipping samples to labora tories);

• Preservation supplies (see the “Sample Bottles and Pr eservation” Section);

• Coolers;

• Garbage bags;

• Packing material;

• Strapping tape; and

• Traffic Report (will be provided by ERG).Sampling Points

The plant must collect samples once per month for four months, based on the schedule specified in the letter. Samples are to be collected fr om each of the three sampling points included in the EPA’s sampling episode. Figure 1 identifies e ach of the sampling points for this sampling program. The following is a description o f the three sampling points:

• FGD wastewater treatment influent (FGD scrubber purge) (SP-1) : This sampling point shall represent the FGD purge stream (e.g., hydroclone overflow) transferred to the FGD wastewater treatment system pri or to any commingling with other wastewaters or treatment system recycle s treams. This sample should be collected from the sample tap on the pipe that flow s from the purge tank to the equalization tank.

• FGD bioreactor influent (SP-2) : This sampling point shall represent the effluent from the chemical precipitation system and the influent to the biological treatment system (prior to nutrient addition). This sampling point s hould be collected from the sample tap on the pipe that is downstream of the sa nd filters and the hold tank, but upstream of the heat exchanger.

• FGD wastewater treatment effluent (SP-3) : This sampling point shall represent the effluent from the biological treatment system, pri or to mixing with dilution water or other streams. This sampling point should be col lected from the sample tap that is located on the pipe downstream of the secon d-stage bioreactor cells.

Analytes

The analytes included in this sampling program include all ana lytes from EPA’s sampling program, except for the dissolved metals analyses (which includes hexavalent chromium). Table 1 contains the listing of all the an alytes included in the monitoring program, as well as the analytical methods that will be used to analyze the samples.Table 1. Analytes and Analytical Methods Included in the Moni toring Program

Parameter Method Number

Classicals Biochemical oxygen demand (BOD 5 ) SM 5210 B Chemical oxygen demand (COD) EPA 410.4 Total suspended solids (TSS) SM 2540 D Total dissolved solids (TDS) SM 2540 C

Sulfate EPA 300.0

Chloride EPA 300.0 Ammonia as nitrogen EPA 350.1 Nitrate/nitrate as nitrogen EPA 353.2 Total Kjeldahl nitrogen (TKN) EPA 351.2 Total phosphorus EPA 365.1 Total cyanide SM 4500 CN E

Total Metals Total mercury EPA 1631E Antimony, arsenic, cadmium, chromium, copper, lead, nickel, selenium, silver, thallium, vanadium, and zinc EPA 200.8 with collision

cell Aluminum, barium, beryllium, boron, calcium, cobalt, ir on, magnesium, manganese, molybdenum, sodium, tin, and titani um EPA 200.7FGD Scrubber Purge(from Purge Tank)LimePolymerEqualizationTankReaction Tank 1ReactionTank 2ReactionTank 3SP-1SP-2Indicates a Sampling PointFerricChlorideFilter2HoldingTankClarifier 1SludgeStorageTankFilter PressSumpFilterBackwashFilter1Solids to FlyAsh LandfillWastewater FlowSludge FlowIntermittent Wastewater FlowClarifierSludgeMixChamberClarifier 2Filter3Cooling WaterNutrientFirst-StageBioreactors(8)First-StageEffluentStorageSecond-StageBioreactors(8)Second-StageEffluentStorageTo Ash BasinBio Reactor BackflushHydrochloricAcidSP-3Figure 1. Belews Creek FGD Wastewater Treatment System Monitoring Program Sampling PointsSample Bottles and Preservation

Table 2 identifies the sample bottles that are needed fo r collecting samples. The table also identifies the on-site preservation that is requi red for the samples. Please note that the number of sample bottles listed in Table 2 refers t o the number of bottles that will need to be collected from each sampling point for each of the four sets of samples. For the Group II samples, the plant can either preserve the samples with sulfuric acid after sample collection, or the plant can order pre-preserv ed sample bottles.

For the total cyanide samples, the plant should test the wastewater from the sampling points with lead acetate paper (turns black in the presence of sulfide) and potassium iodide starch paper (turns blue/violet in the presence of chl orine). If sulfide is present, the plant will need to dilute the sample with blank water until the sulfide is not detected by the lead acetate paper. If chlorine is present, then t he plant will need to add sodium arsenite until the chlorine is not detected by the potass ium iodide starch paper. After any dilution and/or sodium arsenite is added to the sample, the plant will need to preserve the sample with sodium hydroxide until the sample reaches a pH of 10 S.U. Please see ASTM Method D 7365-09a for more details on the preservation requirements for total cyanide.

Table 2. Summary of Sample Container and Planned Preservation

Parameter Sample Container

and Volume On-Site Preservation

BOD 5 One 1-L HDPE

bottle ≤ 6 ° C

Group I a One 1-L HDPE

bottle ≤ 6 ° C

Group II b Two 1-L HDPE

bottles H 2 SO 4 to pH <2, ≤ 6 ° C

Total cyanide One 1-L HDPE

bottle Dilution until sulfide is not detected,

NaAsO 2 until total chlorine is not present, NaOH to pH >10, ≤ 6 ° C

Total metals (EPA Method 200.8 with collision cell) One 500-mL HDPE

bottle None

(acid preserve at laboratory)

Total metals (EPA Method 200.7) One 500-mL HDPE

bottle None

(acid preserve at laboratory)

Total mercury:

Laboratory composite grab samples at

bioreactor influent and bioreactor effluent Four 125-mL glass

bottles

Influent samples and field blank samples Two 250-mL glass

bottles None

(acid preserve at laboratory)

(a) Group I includes TSS, TDS, sulfate, and chloride. (b) Group II includes ammonia as nitrogen, COD, nitrate/nit rite as nitrogen, TKN, and total phosphorus. NOTE: The number of sample bottles refers to the number of sample bottles needed for each sampling point for each of the four sets of samples.Sample Labeling

Label each bottle prior to collecting the sample so i t can be identified by the laboratory. Each self-adhesive label must be completed in indelible ink and must contain the following information:

• Sample number (see Table 3);

• Sampling episode number (see Table 3);

• Sampling point/description (see Table 3);

• Date of sample collection;

• Analysis to be performed;

• Sample bottle type; and

• Required on-site preservation.

If any of the information is incorrect, the plant must revise the label using indelible ink. Once applied to the sample container, the plant must co ver the labels with clear tape to prevent tampering, abrasion, smearing, or loss during trans it. For metal and mercury samples, do not place labels directly on the sample bot tles because of the potential for contamination. Instead, place the label on the outer pl astic bag of the sample bottle. To ensure that the sample label does not become separated from the bottle, the doublebagged sample bottle should be placed in an additional Zi ploc bag after collection.

Table 3 provides the sampling point descriptions, sample numbe rs, and sampling episode number for the plant for this monitoring program. The info rmation in the table should be provided on the sample bottle labels for the appropriate bottles. The “analysis to be performed” should be shown on the label as the followi ng, depending on the specific analysis:

• BOD;

• Group I;

• Group II;

• Total Cyanide;

• Total Metals – 200.8 w/ CC;

• Total Metals – 200.7;

• Total Mercury (for influent and field blank samples);

• Total Mercury – Grab 1 (for bioreactor influent and bioreacto r effluent laboratory composite samples. The bottles should be l abeled as Grab 1, Grab 2, Grab 3, and Grab 4 for the four respective collec tion times).

The “sample bottle type” should be shown on the label t he same as the “Sample Container and Volume” column in Table 2, except that the quantity should not be included. For example, for total mercury, the “sample bo ttle type” should be “250-mL glass bottle.” The “required on-site preservation” sh ould be shown on the label the same as the “On-Site Preservation” column in Table 2, exce pt that “(acid preserve at laboratory)” does not need to be included for the total me tals and total mercury sample

bottles.Table 3. Sampling Point Descriptions and Sample Numbers for Monitoring Program

Sampling Point Description Sample Number Sampling Episode Number

FGD Wastewater Treatment Influent – Set 1 71991 6565

FGD Wastewater Treatment Influent – Set 2 71992 6565

FGD Wastewater Treatment Influent – Set 3 71993 6565

FGD Wastewater Treatment Influent – Set 4 71994 6565

FGD Bioreactor Influent – Set 1 71995 6565

FGD Bioreactor Influent – Set 2 71996 6565

FGD Bioreactor Influent – Set 3 71997 6565

FGD Bioreactor Influent – Set 4 71998 6565

FGD Bioreactor Effluent – Set 1 71999 6565

FGD Bioreactor Effluent – Set 2 72000 6565

FGD Bioreactor Effluent – Set 3 72001 6565

FGD Bioreactor Effluent – Set 4 72002 6565

FGD Wastewater Treatment Influent Field Blank 72003 6565

FGD Bioreactor Influent Field Blank – Set 1 72004 6565

FGD Bioreactor Influent Field Blank – Set 2 72005 6565

FGD Bioreactor Influent Field Blank – Set 3 72006 6565

FGD Bioreactor Influent Field Blank – Set 4 72007 6565

FGD Bioreactor Effluent Field Blank – Set 1 72008 6565

FGD Bioreactor Effluent Field Blank – Set 2 72009 6565

FGD Bioreactor Effluent Field Blank – Set 3 72010 6565

FGD Bioreactor Effluent Field Blank – Set 4 72011 6565

QC Samples

The plant is required to collect field blank samples as part of the sampling program. The field blank samples should be collected at the frequency specified in Table 4.

Table 4. Field Blank Collection Frequency

Sampling Point Total Mercury Total Metals (200.8 and 200.7) Classicals 1

FGD Wastewater

Treatment Influent Collected during one

of the four sets Collected during one

of the four sets No field blanks

required FGD Bioreactor Influent Collected during all

four sets Collected during all

four sets No field blanks

required

FGD Bioreactor Effluent Collected during all

four sets Collected during all

four sets No field blanks

required

1 Classicals includes the analyses for BOD, Group I, Group II, and total cyanide.The laboratory will perform MS/MSD analyses on the total metals and total mercury

analyses; however, no additional sample volume is requi red.

Sample Collection

The plant must use clean sampling techniques when collecti ng the total metals and total mercury samples; therefore, the sampling team should fo llow the clean hands/dirty hands sampling techniques outlined in EPA Method 1669. Additionally, t he plant must try to avoid significant contamination during sample collection, especially from sources such as airborne particles, dirt, and corrosion particulates fr om piping, railing, etc.

The plant must collect grab samples for all analytes a t the influent to the FGD wastewater treatment system. The plant must collect 24-hour compo site samples for all analytes except cyanide and mercury at the bioreactor influent and bio reactor effluent sampling points. The 24-hour composites must be set up to collect equa l sample aliquots every hour over the 24-hour period. For mercury at the bioreactor infl uent and bioreactor effluent sampling points, the plant must collect four individual gra b samples over the 24-hour period (i.e., one mercury grab collected every six hours). For cyanide at the bioreactor influent and bioreactor effluent sampling points, the plan t must collect a single grab sample after the one of the mercury grab samples.

If the plant collects the samples from the same taps used for the collection of samples during the EPA sampling episode, the plant can follow the instructions included in the sampling plan drafted for the EPA sampling episode to colle ct the field blank samples, set up the composite containers, and perform the composite pum p-off procedures for the bioreactor influent and bioreactor effluent sampling points . The following instructions can be used to collect the grab samples at the influent to the FGD wastewater treatment system sampling point and for the mercury and cyanide grab s amples at the bioreactor influent and bioreactor effluent sampling points: (NOTE: If a sample tap or valve is not available to collect these samples or if the bioreacto r influent and bioreactor effluent sampling points have intermittent flows which may inter fere with the automatic composite collection, please contact TJ Finseth, (703) 633-1698 to dis cuss possible alternatives.)

1. Arrive at the sampling point location and prepare supplies and bottles for the sample collection.

2. Clean hands and dirty hands put on Tyvek® suits, masks, and powder-free gloves.

3. Dirty hands gets a clear plastic bag and opens it slightl y (touching only the outer part of the bag) so that clean hands can place h ands in the bag and open the bag completely.

4. Clean hands then uses the plastic bag to shroud the samp le tap (note that there should be no flow through the sample tap at this t ime). Clean hands will need to puncture a small hole in the bag using the ta p and dirty hands can cable tie the bag to the tap to prevent it from fall ing during sample

collection.

5. Dirty hands opens the outer bags of the field blank wat er and total mercury and total metals field blank sample bottles. Clean hand s opens the innerbag of the field blank water and unscrews the lid. Clean h ands then opens the inner bag of the total mercury and total metals field bl ank sample bottles. Clean hands pours the blank water into the fi eld blank sample bottles under the shrouding, caps the bottles, and closes the inner bags. Clean hands then places the total mercury and total met als bottles in the outer bags and dirty hands closes the outer bag.

6. Dirty hands then opens the valve to the sample tap and pur ges the tap for at least two minutes, then keeps the valve open until all sam ples have been

collected.

7. Dirty hands opens the outer bag for the total mercury s ample bottle. Clean hands takes the sample bottle and inner bag and holds the m under the shroud. Clean hands then opens the inner bag, opens the l id of the bottle and fills the total mercury sample bottle. Clean hands caps the sample bottle, closes the inner bag, and places the sample bo ttle in the outer bag. Dirty hands closes the outer bag. The samplers repea t this procedure for the collection of the total metals samples (both EPA 200.8 with collision cell and EPA 200.7), unless the plant is collecting the met als samples as composite samples.

8. The samplers then collect the BOD, Group I, Group II, and total cyanide samples. NOTE: the samplers can collect these samp les using the same technique as the mercury and metals samples, or they can remove the plastic bag shrouding and collect directly from the tap.

9. The Group II and total cyanide samples must be preserved prio r to shipment to the laboratories. Use the information provide d in the “Sample

Bottle and Preservation” section of these instruction f or the preservation steps. Additionally, the BOD, Group I, Group II, and tota l cyanide samples should be placed on ice immediately after sample coll ection/preservation.

Sample Packing and Shipment

The following steps should be used when packing and shipping the s amples to the

laboratories.

1. Make sure that each sample bottle has a label, and tha t the label correctly specifies the sample point.

2. Tighten the lid on each filled sample bottle, being car eful not to overtighten the lid. If bottle threads are dirty to w here the lid is impeded from closing, clean the threads on the bottle being caref ul to not introduce contamination into the sample. Clean the sample bottl e with a cloth rag or paper towel.

3. Prior to packaging, place each sample bottle requiring ≤ 6°C preservation

into an ice chest with wet ice to cool.

4. When each sample requiring ≤ 6°C preservation has reached the desired temperature, wrap each glass sample bottle with two layers of “bubble wrap” (or place bottle in two “bubble bags”). The bubble wr ap must fit snugly and completely cover the sample bottle. Enclose each “bubble-wrapped” container and plastic container in an individual sealable plastic freezer bag.

5. Place two garbage bags inside each other in each of the coolers used to ship samples to the laboratories.

6. Place the classicals samples in the garbage bags in th e coolers with proper end up, close the interior garbage bag by tying, or with a tw ist-tie.

7. Add ice to the cooler to keep samples cold during shipment. Ar range blue ice or sealed plastic freezer bags filled with wet ice on top of the sample bottles (if samples require ≤ 6°C preservation). If using wet ice, place the ice inside two one-gallon sealable freezer bags. Put at l east 4 × 1⁄2 gallons of ice (4 × 2.5 pounds of ice) in each large cooler and 2 × 1⁄2 gallons of ice (2 × 2.5 pounds of ice) in each small cooler. Use more ice when ambient temperatures are very high. Place the ice inside the sec ond garbage bag.

8. Close the second garbage bag by tying, or with a twist-tie

. 9. Place the metals samples in the garbage bags in a diff erent cooler with proper end up, close the interior garbage bag by tying or wit h a twist-tie. Close the second garbage bag by tying, or with a twist-tie . NOTE: the metals samples are not required to be cooled; however, because the metals and classicals are being analyzed by the same laboratory, the metals can be shipped with the classicals, but the metals samples w ould need to be chilled prior to packing them in the cooler with the clas sicals and ice

would need to be added to the cooler between the interior a nd outer garbage bags to keep the samples cold.

10. Fill in any free space around the bottles in the metals and classicals coolers with additional cushioning material. Sufficient pac king material should be used so that the sample containers will not shi ft during shipment.

11. Fill out and print a traffic report form for the classi cals and metals samples (provided electronically by ERG). Seal the last two pages o f the traffic report form(s) in a plastic envelope secured to the insid e of the top of the cooler(s). NOTE: the top page of the traffic report mus t be sent to ERG at the following address:

Eastern Research Group 14555 Avion Parkway, Suite 200 Chantilly, VA 20151

Attn: TJ Finseth (703) 633-1698

12. Close the cooler(s).

13. Place a completed laboratory address label on the lid o f the cooler(s). The classicals and metals samples should be shipped to TestAme rica as

follows:

TestAmerica

4955 Yarrow StreetArvada, CO 80002 Attn: Elizabeth Eichelberger (303) 736-0100

14. Make several wraps with strapping tape around the cooler pe rpendicular to

the seal to ensure that the lid will remain closed if t he latch is accidentally released or damaged.

15. Place the mercury samples in the garbage bags in a separ ate cooler with proper end up, close the interior garbage bag by tying, or with a twist-tie.

16. Do not add ice to the mercury cooler; simply close the second garbage bag by tying, or with a twist-tie.

17. Fill in any free space around the bottles with additional cushioning material. Sufficient packing material should be used so that the sample containers will not shift during shipment.

18. Fill out and print a traffic report form for the mercury samples (provided electronically by ERG). Seal the last two pages of the traffic report form in a plastic envelope secured to the inside of the top o f the cooler. NOTE: the top page of the traffic report must be sent to ERG a t the same address provided in step 11:

19. Close the cooler.

20. Place a completed laboratory address label on the lid o f the cooler. The mercury samples should be shipped to Frontier as follows:

Frontier GeoSciences

414 Pontius Ave. North Seattle, WA 98109

Attn: Patrick Garcia-Strickland (206) 957-1428

21. Make several wraps with strapping tape around the cooler pe rpendicular to

the seal to ensure that the lid will remain closed if t he latch is accidentally released or damaged.

22. Fill out the necessary paperwork for FedEx or UPS to prepa re the shipment for pick up or drop off. NOTE: the samples must b e shipped priority overnight to arrive at the laboratories the following morning. Ship

the coolers to the laboratories.

23. After the coolers have been dropped off (or picked up), pleas e contact TJ Finseth at (703) 633-1698, to notify him that the samples have b een shipped to the laboratories.

Traffic Reports

An example traffic report will be provided to the plant by ERG for the first sample collection event. The plant will need to make changes t o the traffic report electronically for the other three sample collection events. Some information, such as the date andsample collection times must be entered by the plant after the sample collection and

therefore, will not be included in the example provided by ERG.

After the traffic report is completed by the plant, th e plant must print the four pages in the file. The last two pages in the file must be placed in t he cooler for shipment to the laboratories and the first page must be sent to ERG. The plant can keep the second page of the traffic report.

Engineering Data

The plant must provide engineering data regarding the operatio n of the plant and FGD systems during the sample collection period. Additionall y, the plant must make some field measurements when samples are collected, including pH , temperature, and visual observations, and provide the data to EPA after the sample collection period. The engineering data and field measurement data requirements are in an Excel® spreadsheet titled “Monitoring Program Engineering Data Tables,” which w ill be provided by ERG.

The tables are also included at the end of this enclosure. The plant must complete the engineering data sheets and field measurement sheets in th e Excel® file and e-mail the completed forms to TJ Finseth at thomas.finseth@erg.com

.

Certification Statement

The individual responsible for directing and supervising the s ample collection and the engineering data preparation must sign the certification statement (provided in Enclosure 4) and submit it upon the completion of the sampling program . The signed certification

statement should be scanned and e-mailed to TJ Finseth at thomas.finseth@erg.com , at the same time the engineering data is submitted.Complete the following tables for each sampling pointPlant NameSampleCollectionNumberDate of SampleCollectionSample CollectionTime Temperature (°C)pH(S.U.)Set 1Set 2Set 3Set 4Plant NameSampleCollectionNumberInfluent SamplesCollected asGrabs(Yes or No)Mercury and CyanideSamples Collected asGrabs(Yes or No)Bioreactor Influentand BioreactorEffluent SamplesCollected as 24-HourComposites(Yes or No)Tyvek Suitsused(Yes or No)Dust MasksUsed forMercury(Yes or No)Clean Hands/DirtyHands SamplingTechniques Used(Yes or No)Description of SampleCollection Technique (ifdifferent thaninstructions)Description of AbnormalConditions in FGD Systemor FGD WastewaterTreatment System that MayImpact ConcentrationsSet 1Set 2Set 3Set 4Complete the following tables based on the plant operating characteristics during each set of samplescollectedUnits OperatingDuring SamplingDayUnits Off-lineEntireSampling DaySCRs/SNCRsOperating onUnitsSet 1Set 2Set 3Set 4Flow Rate (gpm) DurationSet 1Set 2Set 3Set 4Lime Usage(tons)Ferric ChlorideUsage(Liters/day)Organosulfide Usage(Liters/day)Polymer Usage(Liters/day)Acid Usage(Liters/day)ChemicalPrecipitationSystem EffluentFlow Rate (gpd)Dilution WaterAddition Priorto BiologicalTreatmentSystem(gpd)BiologicalTreatmentSystem EffluentFlow Rate (gpd)Set 1Set 2Set 3Set 4Plant NameDate of SampleCollectionSampleCollectionNumberPlant Operation During Sample CollectionFGD Wastewater Treatment Operation During Sample CollectionPlant NameDate of SampleCollectionSampleCollectionNumberScrubber PurgeFlow Rate DuringInfluent SampleCollection(gpm)Percent HydrocloneOverflow RecycledBack to ScrubberPlant NameSampleCollectionNumberDate of SampleCollectionScrubber Slurry Blowdown FlowRateScrubber SlurryPercent SolidsPlant Operation During Sample CollectionUnit 1 Unit 2 Daily Power Generation (MW-hrs)

Plant Name Date Provide the daily power generation for each scrubbe d unit starting two weeks prior to the first set of samples through the last set of samplesChemical Precipitation

Effluent Dilution Water

Addition Prior to Biological

Treatment System Biological Treatment

System Effluent Plant Name Date FGD Wastewater Treatment System Flow Rates (gpd) Provide the average flow rate in the FGD wastewater treatment system for each stream included in the table starting two weeks prior to the first set of samples through the last set of samples